Field of invention
[0001] The present invention is related to an improved method for Atomic Layer deposition.
Further, it is also related to a reactor design suitable for applying the method.
Background
[0002] Because in the field of electronics in general further downscaling of the semiconductor
devices is always proceeding, deposition processes have to be developed able to deposit
layers with a thickness control at atomic layer scale.
[0003] One of these deposition techniques is Atomic Layer Deposition (ALD), often used for
depositing dielectric layers.
[0004] Atomic Layer Deposition is a thin film deposition technique based on the use of separated
chemisorption reactions of at least two gas phase reactants with a substrate.
[0005] There are two characteristics which can limit the quality and scalability of layers
deposited by ALD. A first characteristic is the growth-per-cycle (GPC), which often
is much lower than the theoretical maximum of one monolayer per cycle. This can result
in film roughness and slow film closure, which makes especially thin films (thinner
than about 5 nm) prone to localized defects such as pinholes.
[0006] A second characteristic is the presence of impurities due to unreacted precursor
ligands.
[0007] For example, in the deposition of hafnium oxide from hafnium tetrachloride and water,
the growth-per-cycle is only 20% of a monolayer and the Cl-impurities remain in the
deposited layer.
Aim of the invention
[0008] The present invention aims to provide an ALD method and reactor to fabricate a high-quality
ALD layer under optimized process conditions.
Summary of the invention
[0009] The present invention provides an ALD method comprising the steps of:
- a) providing a semiconductor substrate in a reactor
- b) providing a pulse of a first precursor gas into the reactor at a first reactor
temperature,
- c) providing a first pulse of a second precursor gas into the reactor at a second
temperature,
- d) providing a second pulse of the second precursor gas at a third temperature lower
than the second temperature, and
- e) optionally, repeating at least once step b) through step d) till a desired layer
thickness is achieved.
[0010] The first precursor gas can be a halide or an oxyhalide such as POCl
3, and more particularly it can be a metal halide or a metal oxyhalide such as HfCl
4, TaCl
5, WF
6, WOCl
4, ZrCl
4, AlCl
3, TiCl
4, SiCl
4 or the like.
[0011] The second precursor gas can be any precursor able to decompose the first precursor,
or to eliminate the ligands of the first precursor. More particularly it can be H
2O, H
2O
2, O
2, O
3, NH
3, H
2S, H
2Se, PH
3, AsH
3, C
2H
4 or Si
2H
6.
[0012] In a method according to the invention said first temperature can be between about
100°C and about 800°C, preferably between about 150°C and about 650°C, or between
about 200°C and about 500°C, or more preferably between about 225°C and about 375°C.
[0013] In a method according to the invention said second temperature can be substantially
equal or higher than the first temperature, more particularly between about 100°C
and about 800°C, preferably between about 150°C and about 650°C, or between about
200°C and about 500°C, or more preferably between about 225°C and about 375°C.
[0014] In a method according to the invention said third temperature can be substantially
lower than the second temperature, preferably lower than about 500°C, or than about
350°C, or than about 225°C and more preferably is room temperature.
[0015] A method according to the invention can further comprise the step of heating the
substrate surface at a fourth temperature, between step c) and d).
[0016] In a method according to the invention said fourth temperature can be substantially
equal or higher than the second temperature, preferably higher than about 375°C and
more preferably equal to about 500°C.
[0017] In a method according to the invention, the step of heating the substrate surface
at a fourth temperature can be performed in inert atmosphere.
[0018] In a method according to the invention, the substrate can be exposed to a plasma
treatment during and/or after step d).
[0019] The plasma used for said plasma treatment can consist of N
2O, NO, O
2, N
2, H
2, NO
2, or NH
3, etc.
[0020] In a preferred method according to the invention the first and second temperature
is about 300°C, the third temperature is room temperature and the fourth temperature
(if any) is about 500°C.
[0021] The present invention also provides an ALD reactor suitable for carrying out a method
according to the invention.
[0022] Such an ALD reactor comprises:
- i. a first and a second susceptor,
- ii. means for heating a substrate when present on the first susceptor, and
- iii. means for cooling the substrate when present on the second susceptor.
[0023] The reactor according to the invention can further comprise means for transporting
a semiconductor substrate between both susceptors.
[0024] The reactor according to the invention can further comprise means for producing a
plasma.
Short description of the drawings
[0025] Figure 1: Effect of the H
2O pulse length on the GPC as determined by RBS (Rutherford Backscattering Spectroscopy).
[0026] Figure 2: Effect of the H
2O pulse length on the TOFSIMS (Time-Of-Flight Secondary Ion Mass Spectroscopy) Cl-profile.
[0027] Figure 3: Growth-per-cycle (RBS) as a function of the number of cycles for HfO
2 on 1 nm chemical oxide substrates.
[0028] Figure 4: Decay of the TOFSIMS Si intensity as a function of the RBS Hf-coverage
for HfO
2 deposited with IRPA and standard ALD on chemical oxide substrates, and for standard
HfO
2 on different starting substrates.
[0029] Figure 5: TOFSIMS Cl-profiles of HfO
2 deposited with different extended reaction cycles (a) and after different post deposition
anneals (b).
[0030] Figure 6: TOFSIMS Cl-profiles of HfO
2 deposited with intermediate cooling and longer H
2O pulses.
Description of the invention
[0031] Atomic Layer Deposition (ALD) is a thin film deposition technique based on the use
of separated chemisorption reactions of at least two gas phase reactants with a substrate.
Such gas phase reactants are also called precursor gasses.
[0032] There are two characteristics which can limit the quality and scalability of layers
deposited by ALD.
[0033] A first characteristic is the growth-per-cycle (or growth rate), which is often much
lower than the theoretical maximum of one monolayer per cycle. This can result in
film roughness and slow film closure, which makes especially thin films (on the order
of less than 5 nm) prone to localized defects such as pinholes.
[0034] A second characteristic is the presence of impurities due to unreacted precursor
ligands.
[0035] In order to optimize the above characteristics, the present invention provides an
ALD method comprising the steps of:
- a) providing a semiconductor substrate in a reactor,
- b) providing a pulse of a first precursor gas into the reactor at a first temperature,
- c) providing a first pulse of a second precursor gas into the reactor at a second
temperature,
- d) providing a second pulse of the second precursor gas at a third temperature lower
than the second temperature, and
- e) optionally repeating at least once step b) through step d) till a desired layer
thickness is achieved.
[0036] The semiconductor substrate can comprise or can consist of any semiconductor material(s)
suitable in the field of IC processing. In particular it can comprise or can consist
of silicon, germanium or silicon germanium.
[0037] The layer obtainable by a method according to the invention can be of a substantially
pure element (e.g. Si, Cu, Ta, W), an oxide (e.g. SiO
2, GeO
2, HfO
2, ZrO
2, Ta
2O
5, TiO
2, Al
2O
3, PO
x, VO
x, CrO
x, FeO
x, ZnO, SnO
2, Sb
2O
5, B
2O
3, In
2O
3, WO
3), a nitride (e.g. Si
3N
4, TiN, TaN
x, AlN, BN, GaN, NbN, Mo
xN, W
xN), a carbide (e.g. SiC), a sulfide (e.g. CdS, ZnS, MnS, WS
2, PbS), a selenide (e.g. CdSe, ZnSe), a phosphide (e.g. GaP, InP), an arsenide (e.g.
GaAs, InAs), or mixtures thereof.
[0038] The first precursor gas can be a halide or an oxyhalide such as POCl
3. More particularly it can be a metal halide or a metal oxyhalide. For example, said
first precursor can be HfCl
4, TaCl
5, WF
6, WOCl
4, ZrCl
4, AlCl
3, , TiCl
4, SiCl
4 or the like.
[0039] The second precursor gas can be any precursor able to eliminate the ligands of the
first precursor. More particularly it can be H
2O, H
2O
2, O
2, O
3, NH
3, H
2S, H
2Se, PH
3, AsH
3, C
2H
4 or Si
2H
6.
[0040] In the context of the invention the first, second and third temperature is to be
understood as the temperature in the reactor, unless otherwise stated.
[0041] In a method according to the invention the first temperature can be between (about)
100°C and (about) 800°C, preferably between (about) 150°C and (about) 650°C, or between
(about) 200°C and (about) 500°C, and more preferably between (about) 225°C and (about)
375°C.
[0042] In a method according to the invention the second temperature can be substantially
equal or higher than the first temperature, between (about) 100°C and (about) 800°C,
preferably between (about) 150°C and (about) 650°C, or between (about) 200°C and (about)
500°C, and more preferably between (about) 225°C and (about) 375°C.
[0043] In a method according to the invention the third temperature can be substantially
lower than the second temperature, preferably lower than (about) 500°C, or lower than
(about) 350°C, or lower than (about) 225°C and more preferably is room temperature.
[0044] A method according to the invention can further comprise the step of heating the
substrate surface at a fourth temperature, between step c) and d).
[0045] In a method according to the invention this fourth temperature can be substantially
equal or higher than the second temperature, higher than (about) 375°C and preferably
equal to (about) 500°C.
[0046] Said step of heating the substrate surface at a fourth temperature can be performed
in inert atmosphere, such as but not limited to nitrogen or argon.
[0047] In a method according to the invention, the substrate can be exposed to a plasma
treatment during and/or after step d). The plasma can be direct or remote.
[0048] Said plasma can consist of N
2O, NO, O
2, N
2, H
2, NO
2, or NH
3, etc.
[0049] In a preferred method according to the invention the first and second temperature
is (about) 300°C, the third temperature is room temperature and the fourth temperature
is (about) 500°C.
[0050] The invention provides also a new reactor design that is suitable for performing
the method of the invention and in which reactions can be performed at their optimized
temperature.
[0051] Such an ALD reactor comprises:
- a first and a second susceptor,
- means for heating a substrate when present on the first susceptor, and
- means for cooling the substrate when present on the second susceptor.
[0052] In the framework of the invention, a susceptor is any means, e.g. a plate, suitable
for supporting (bearing) the substrate upon which the layer is to be deposited.
[0053] The ALD reactor according to the invention can further comprise means for transporting
a semiconductor substrate between both susceptors.
[0054] The ALD reactor according to the invention can further comprise means for producing
a plasma.
[0055] According to the invention, the means for heating can comprise flash lamps or any
means to create a temperature increase of at least the substrate surface.
[0056] According to the invention, the means for cooling can comprise a recirculating cooling
medium, such as cooled nitrogen, or a Peltier element or any means to create a temperature
decrease of at least the substrate surface.
[0057] In a particular embodiment according to the present invention, a hafnium oxide layer
can be deposited using a method of the invention wherein hafnium tetrachloride is
the first precursor gas and water the second precursor gas.
[0058] More particularly, an ALD method for depositing an hafnium oxide layer can comprise
the steps of:
- i. providing a semiconductor substrate in the ALD reactor,
- ii. providing a pulse of HfCl4 in the reactor at 300°C,
- iii. providing a first pulse of H2O in the reactor at 300°C,
- iv. optionally heating the substrate at 500°C in N2 atmosphere,
- v. providing a second pulse of H2O in the reactor at room temperature, while the substrate can be exposed to an N2O plasma treatment, and
- vi. optionally, repeating at least once step ii) through step v).
[0059] The reaction cycle (step (ii) through step (v)) can then be repeated until the desired
layer thickness is obtained.
[0060] The step of providing the second pulse of H
2O can also comprise exposure to moisture present in the reactor.
[0061] The steps of providing a pulse of HfCl
4, providing a first pulse of H
2O and heating the substrate can be performed on the first susceptor. The temperature
is maintained constant at (about) 300°C. Heating means, e.g. (flash) lamps, are provided
for fast wafer surface temperature increase from (about) 300°C to (about) 500°C when
the substrate is present on the first susceptor.
[0062] Then the substrate is transported from the first to the second susceptor.
[0063] The second H
2O pulse (which can comprise moisture exposure during transportation in this case)
and optionally plasma exposure can be performed on the second susceptor at lower temperature.
Cooling means are provided for wafer surface temperature decrease below (about) 225°C
or even to room temperature.
[0064] By means of conventional ALD, the deposition of hafnium oxide from hafnium tetrachloride
and water, the growth-per-cycle is only 20% of a monolayer and the Cl-impurities remain
in the deposited layer.
[0065] By means of the method according to the invention, the growth-per-cycle can be enhanced
from 15% to 40% of a monolayer and the Cl-content can be reduced by 2 orders of magnitude.
[0066] Though the following example describes only the deposition of HfO
2 from HfCl
4 and H
2O, it is to be understood that said first and second precursors as defined in the
present invention are expected to follow the same chemical mechanisms as described
in the example section, when carrying out a method of the invention. Therefore, the
present invention is not intended to be limited to the following illustrative example.
Example
[0067] Atomic Layer Deposition (ALD) is based on the use of separated chemisorption reactions
of at least two gas phase reactants with a substrate.
[0068] For the deposition of HfO
2 from HfCl
4 and H
2O, HfCl
4, which is the first precursor, chemisorbs on the substrate by reaction with surface
-OH groups:
x OH* + HfCl
4 → O
xHfCl
4-x* + x HCl
[0069] The chemisorption must be self-limiting and saturated within the time of the precursor
pulse. When full saturation is reached, the excess of HfCl
4 and the gas reaction byproducts are purged away by an nitrogen flow, further referred
to as a nitrogen purge. Thereafter, pulse and nitrogen purge steps are repeated with
the H
2O precursor in order to hydrolyze the Hf-Cl bonds.
O
xHfCl
4-x* + (4-x) H
2O → O
xHf(OH)
4-x + (4-x) HCl
[0070] This sequence is repeated until the desired HfO
2 film thickness is obtained.
[0071] Usually, the growth-per-cycle is less than 1 monolayer because of the following limitations:
either the number of reactive sites on the substrate is limited, or steric effects
from bulky precursors limit the amount of material to be chemisorbed.
[0072] Moreover, the growth-per-cycle can depend on the starting substrate - when the substrate
changes from the starting substrate (for example silicon substrate) to the deposited
material itself. When starting substrate effects have vanished, the growth-per-cycle
becomes constant and is referred to as the steady growth-per-cycle.
[0073] Furthermore, the growth-per-cycle can depend on the temperature of the deposition.
[0074] For the conventional HfCl
4/H
2O process (also referred to as Standard HfCl
4/H
2O ALD process), the steady growth-per-cycle at 300°C is only 15% - 17 % of a monolayer
(also referred to as oML). Several experimental observations indicate that the low
HfO
2 growth-per-cycle is caused by limitation of the number of reactive sites, the -OH
groups in the HfCl
4 reaction.
[0075] For example, the decreasing growth-per-cycle as a function of temperature is attributed
to decreased hydroxylation of the HfO
2 surface. This implies that the HfCl
4 reaction with oxygen bridging sites is not very efficient. Indeed, it has been shown
that the ZrCl
4 species (the HfCl
4 and ZrCl
4 chemistries are very similar) are not very reactive towards siloxane bridges, since
the preheating temperature of the support influences the amount of adsorbed Zr.
[0076] Furthermore, substrate inhibition occurs typically on surfaces with too low -OH density,
for example HF cleaned Si.
[0077] As an illustration of several embodiments of the present invention, an ALD reaction
cycle with different intermediate treatments, such as exposure to gas phase moisture,
plasma treatments or thermal anneals is studied and compared to the Standard ALD cycle.
[0078] In the case of an ALD cycle with plasma treatments, which is a particular embodiment
of the present invention, this extended ALD process is also referred to as Intermediate
Remote Plasma Assisted (IRPA) ALD.
[0079] In the case of an ALD cycle with a thermal anneal, which is also a particular embodiment
of the present invention, this extended ALD process is also referred to as Intermediate
Thermal Anneal (ITA) ALD.
[0080] A first goal is to increase the number of -OH groups at the HfO
2 surface, in order to enhance the growth-per-cycle. A theoretical model predicts that
the higher the growth-per-cycle, the lower the number of cycles required for film
closure and the lower the roughness of the film. Therefore, the improvement of the
quality and scalability of HfO
2 layers by enhancing the growth-per-cycle with intermediate treatments is investigated.
[0081] A second goal is to reduce the Cl-content of the HfO2 layers. Indeed, the intermediate
treatments can affect the growth-per-cycle and the Cl-content.
[0082] All samples are processed in a Polygon 8200 cluster. Prior to deposition, a chemical
oxide of 1 nm thickness is grown. HfO
2 is deposited in an ALDTM Pulsar 2000 reactor, a hot wall cross-flow type reactor
with inert gas valving. The pressure in the reactor is 1.33 mbar (1 Torr). All pulses
with HfCl
4 precursor and first pulses with H
2O precursor are performed at 300°C. HfCl
4 is a solid at room temperature. It is heated to approximately 185°C to achieve sufficient
vapor pressure for the HfCl
4 pulses. The pulse and inert gas purge times for the Standard process are indicated
in Table 1. Elongation of the purge times after HfCl
4 or H
2O pulses up to 5 minutes does not change the growth-per-cycle, suggesting that the
precursor pulses are well separated in the standard conditions. Moreover, this indicates
that there is sufficient recovery time of the HfCl
4 solid source between different pulses.
Table 1: Pulse and inert gas purge parameters in the standard HfO
2 deposition.
HfCl4 pulse (s) |
0.1 |
N2 purge (s) |
1 |
H2O pulse (s) |
0.3 |
N2 purge (s) |
3 |
[0083] Samples are measured by spectroscopic ellipsometry (SE) on a KLA-Tencor ASET F5.
RBS is performed in a RBS400 end station (Charles Evans and Associates) with a 1 MeV
He+ beam. TOFSIMS depth profiles are measured with an IonTOF-IV instrument using a
dual beam set-up with a 500 eV Ar+ ion beam.
[0084] Intermediate treatments are performed in an Epsilon Nitride CVD (Chemical Vapor Deposition)
reactor, equipped with a remote Microwave Radical Generator (MRG) or in the transport
module of the polygon cluster.
[0085] The steady growth-per-cycle for the Standard HfCl
4/H
2O ALD process at 300°C (as described in Table 2) is 1.4 Hf/nm2 or 15% of a monolayer
(figure 1), in agreement with literature. The growth-per-cycle is not fully saturated
with the standard H
2O pulse of 0.3 seconds, as shown in figure 1. The growth-per-cycle saturates at a
H
2O pulse of about 10 seconds to a value of 20% of a monolayer. Also the Cl-content
is saturated at 10 seconds, as shown by TOFSIMS (figure 2). The growth-per-cycle does
not depend on the HfCl
4 pulse length.
[0086] The effect of the 1 nm chemical oxide substrate on the growth-per-cycle for Standard
HfCl
4/H
2O ALD compared to IRPA ALD is shown in figure 3. In the first reaction cycle, the
growth-per-cycle is almost 3 times higher than the steady growth-per-cycle (4.3 Hf/nm2
or 47% of a monolayer) in agreement with literature. The substrate enhancement only
acts in the first reaction cycle. This is surprising, as the chemical oxide substrate
can by no means be fully covered by HfO
2 in the first cycle, as less than half a ML is deposited. Therefore, one would expect
to see growth enhancement also in the second reaction cycle.
[0087] One possible explanation is that all Si-OH groups on the chemical oxide are consumed
by reaction with HfCl
4 in the first reaction cycle. Any Si-O-Si bridges left uncovered by HfO
2 are not hydrolyzed in the H
2O pulse of the first reaction cycle. Therefore, HfO
2 in the second reaction cycle only reacts with the Hf-OH groups and the steady HfO2
growth-per-cycle is immediately reached. This would imply that, as the Si-O-Si sites
are not reactive towards both HfCl
4 and H
2O precursors, no further growth is possible from the substrate; only sideward growth
from HfO
2 islands is possible to cover that area.
[0088] Another possibility is that both Si-OH and Si-O-Si bridges react with HfCl
4. The reaction with the latter surface sites results in contamination of the Si substrate
by Cl:
Si-O-Si* + HfCl
4 → Si-O-HfCl
3* + Si-Cl
[0089] Si-Cl bonds are difficult to hydrolyze at 300°C. Therefore, in the next reaction
cycles HfO
2 deposition on the Si-Cl sites is blocked. This would explain the larger Cl-content
at the bottom interface of HfO
2 layers. The fact that the HfO
2 growth-per-cycle remains constant in the subsequent reaction cycles, and the decrease
in Cl-content could indicate that nucleation on the HfO
2 substrate proceeds only on the Hf-OH groups, and that Hf-O-Hf bridges are less reactive
than Si-O-Si bridges.
[0090] Plasma treatment every cycle enhances the steady growth-per-cycle from 15% of a monolayer
to 42% of a monolayer (figure 3 and table 2).
[0091] A theoretical model for random deposition in ALD predicts that the higher the growth-per-cycle,
the smaller the number of cycles required for film closure and the lower the roughness
of the film. The growth mode of HfO
2 layers with different growth-per-cycle can be investigated by TOFSIMS surface measurements.
The decay of the Si substrate intensity is plotted as a function of the Hf-coverage
from RBS (figure 4).
[0092] Indeed, a faster decay of the TOFSIMS Si intensity for IRPA ALD HfO
2 as compared to Standard ALD HfO
2 (figure 4). The difference with Standard HfO
2 ALD is small but systematic.
[0093] In table 2 the GPC (% ML) for different extended reaction cycles is shown. The Hf-coverage
is measured by RBS or SE on samples with 10 reaction cycles. The growth-per-cycle
is calculated as the average over the last 9 reaction cycles to exclude the enhancement
effect of the substrate in the first reaction cycle.
Table 2: Growth-per-cycle for different reaction cycles.
|
Description of the reaction cycle |
GPC RBS (Hf/nm2) |
GPC RBS (% ML) |
GPC SE (% ML) |
1 |
Standard |
1.40-1.50 |
15 - 16 % |
18 - 20 % |
2 |
Standard + RT plasma treatment |
4.10 |
42 % |
49 % |
3 |
Standard + 5 min cooling |
3.21 |
34 % |
40 % |
4 |
Standard + 90 sec cooling |
2.89 |
32 % |
35 % |
5 |
Standard + 2 min 420°C + 2 min cooling |
2.95 |
32 % |
35 % |
6 |
HfCl4 pulse + 4 min cooling |
0.85 |
9 % |
12 % |
7 |
HfCl4 pulse + 2 min 420°C + 4 min cooling |
0.88 |
10 % |
11 % |
[0094] Growth enhancement is also observed for room temperature treatments without plasma
(table 2 reaction cycle 3 and 4). The growth-per-cycle (34% of a monolayer) is slightly
lower as compared to the RT (room temperature) remote plasma treatments (table 2 reaction
cycle 2) (42% of a monolayer). Thus, an important contribution of the growth enhancement
during plasma treatments comes from lowering the temperature. Therefore, one could
suggest that the enhanced growth is caused by H
2O adsorption when the wafer is cooled down to room temperature:
Hf-O-Hf* + H
2O → 2 Hf-OH*
[0095] It has been shown that for moisture concentrations as low as 10-100 ppm are sufficient
for monolayer coverage of H
2O on HfO
2 at room temperature. Thus, the moisture background in the transport module could
suffice for the introduction of -OH groups during the transport from ALD to nitride
reactor and back. The adsorption of H
2O in the transport module saturates within 90 seconds: similar growth enhancement
is achieved for 90 seconds or 5 minutes intermediate cooling.
[0096] Support for the H
2O reaction in the transport module comes from the observation that HfO
2 can be deposited without H
2O pulse in the ALD reactor at 300°C, but with intermediate cooling in the transport
module instead (Table 2 reaction cycle 6 and 7). Probably, the Cl-content of this
HfO
2 layer is very high, as the Cl removal becomes more difficult at lower temperatures.
The expected high Cl-content might explain why the growth-per-cycle for this process
is slightly lower than for the standard ALD process.
[0097] The growth-per-cycle is also enhanced for intermediate anneal at 420°C in the nitride
reactor (table 2 reaction cycle 5), with the same amount as for intermediate cooling
(table 2 reaction cycle 3 and 4). One would expect that the -OH density on the HfO
2 substrate decreases by thermal treatment, and as such, the growth-per-cycle is decreased.
This probably indeed occurs during the intermediate anneal. However, the intermediate
anneal is performed in the nitride reactor on the polygon platform, and the transport
from nitride to ALD reactor takes about 2 minutes. As shown above, the HfO
2 surface can easily re-adsorb moisture during the cooling that occurs during this
transport.
[0098] Analysis of the Cl content in HfO
2 layer can give more information on the ALD reaction mechanism because it shows the
efficiency of Cl-removal by the H
2O reaction and/or the intermediate treatments applied after the H
2O reaction. TOFSIMS Cl-profiles of standard HfO
2 are therefore compared with HfO
2 deposited with the different extended reaction cycles (figure 5 and figure 6). The
intermediate treatments are applied only every 10 reaction cycles instead of after
every single reaction cycle in order to speed up the deposition of 4 nm HfO
2 layers (minimum thickness to obtain a reasonable Cl-profile). The effect of the intermediate
treatment on the Cl content is still apparent in the Cl-profiles (figure 5 and figure
6).
[0099] One can see that HfO
2 deposited with plasma treatments or cooling in moisture contains about twice as much
Cl as the Standard HfO
2 process (figure 5 and figure 6). Apparently, the standard H
2O pulse of 0.3 seconds is too short to hydrolyze the much larger amount of Hf-Cl bonds,
introduced by the enhanced growth-per-cycle. Therefore, the H
2O pulse time is re-optimized for the enlarged growth-per-cycle. H
2O pulses of 10 seconds are sufficient to reduce the Cl-content too a similar level
as for the process without intermediate cooling (Figure 6).
[0100] Cl can efficiently be removed by intermediate thermal treatments (figure 5 (a)).
The temperature and frequency of the intermediate anneal determines the efficiency
of the Cl-elimination. A reduction of 2 orders of magnitude is obtained with intermediate
anneals at 500°C every 10 cycles. On the other hand, the Cl-content is not reduced
during a post deposition anneal at 500°C (Figure 5 (b)). For intermediate thermal
anneals at 420°C every 10 cycles, the Cl-content is reduced as compared to intermediate
cooling, but the Cl-level is still at the same level as for the standard HfO
2 process. Applying a longer H
2O pulse gives in this case a larger improvement. The ambient of the intermediate anneal
(O
2 or N
2) does not influence the Cl-content of the layers. However, it can have a significant
impact on the thickness of the interfacial layer. For O
2 anneals at 500°C, the interfacial oxide easily grows to more than 1 nm.
[0101] The following HfCl
4/H
2O ALD reaction mechanism can be proposed.
[0102] Having regard to HfCl
4 reaction, in agreement with literature, it is proposed that HfCl
4 reacts with -OH groups and not with Hf-O-Hf bridges:
x OH* + HfCl
4 → O
xHfCl
4-x* + x HCl
[0103] All experimental observations in this work support that in the standard process,
the amount of Hf deposited in this half reaction is controlled by the number of -OH
groups on the substrate, and not by steric hindrance of the -Cl ligands.
[0104] This is further investigated by using a recent model of growth-per-cycle (Table 3).
The model is based on the mass balance of chemisorption and assumes a two-dimensional
arrangement of the adsorbed ligands.
[0105] For the standard HfO
2 process, the growth-per-cycle is 1.4 Hf/nm2 for plasma treatments [Table 2]. During
the HfCl
4 reaction, each Hf atom brings along four Cl ligands (using the HfCl
4 precursor). Thus, according to mass balance, about 5.6 (= 4.1 x 4) Cl ligands /nm2
arrive to the surface. The maximum number of Cl ligands remaining on a flat surface
when steric hindrance prevails can be estimated from the van der Waals radius of Cl
(0.175 nm as 9.4 /nm2). Thus, for the standard process, the amount of Cl after HfCl
4 reaction is still lower than the maximum allowed by steric hindrance. However, the
maximum amount of Cl is most likely slightly lower than this theoretical value because
this upper limit does not consider the specific bond arrangements in the Hf-Cl layer.
Thus for the standard process, the model cannot give much information about the OH
group content of the substrate.
[0106] On the other hand, the model can give some information in case of growth enhancement
with intermediate treatments. The growth-per-cycle is 4.1 Hf/nm2 for plasma treatments
[Table 2]. Thus, according to mass balance, about 16.4 (= 4.1 x 4) Cl ligands /nm2
arrive to the surface. This is much higher than the maximum number of Cl ligands allowed
on a flat surface (9 /nm2). Therefore, at least (16.6 - 9.4) ≈ 7 Cl /nm2 have been
removed by reaction with -OH (Table 3). Thus, this number also is a rough estimation
of the -OH group density on HfO
2 after plasma treatment. For intermediate cooling, the -OH group density calculated
in a similar way is 2-3 /nm2 (Table 3).
Table 3: Amount of -OH groups on HfO
2 for different intermediate treatments after the H
2O ALD half reaction obtained by using the steric hindrance model.
Description of the extended reaction cycle |
# OH (/nm2) |
Standard + RT plasma treatment |
7 |
Standard + 5 min cooling |
3 |
Standard + 90 sec cooling |
2 |
Standard + 2 min 420°C + 2 min cooling |
2 |
[0107] Having regard to H
2O reaction, the HfCl bonds introduced during the HfCl
4 pulse are hydrolyzed in the H
2O reaction:
HfCl
x* + x H
2O → Hf(OH)
x* + x HCl
[0108] At 300°C, this reaction is not complete as some residual Cl is present in the HfO
2 layer even if the H
2O pulse is saturated.
[0109] As the temperature of the H
2O reaction decreases, dissociation of H
2O on oxygen bridges also becomes important:
Hf-O-Hf* + H
2O → 2 Hf-OH*
[0110] An effective way of eliminating Cl is by intermediate thermal annealing after the
H
2O pulse. The Cl-content is independent of the anneal ambient (O
2 or N
2). It is proposed that neighboring Hf-Cl and Hf-OH groups at the top surface react
and release HCl:
HfCl* + HfOH → HfOHf* + HCl
[0111] As such, oxygen bridges are created. It is proposed that this reaction becomes more
important as the temperature of the anneal increases.
[0112] Thus, in order to enhance the growth-per-cycle from 15% to 40% of a monolayer and
to reduce the Cl-content by 2 orders of magnitude, the following extended HfCl
4/H
2O ALD reaction cycle can be proposed:
- HfCl4 reaction at 300°C
- H2O reaction at 300°
- Annealing in N2 for Cl-elimination at 500°C
- Hydroxylation with N2O plasma during and/or after moisture exposure at low temperature.
1. An Atomic Layer Deposition method comprising the steps of:
a) providing a semiconductor substrate in a reactor,
b) providing a pulse of a first precursor gas into the reactor at a first temperature,
c) providing a first pulse of a second precursor gas into the reactor at a second
temperature,
d) providing a second pulse of the second precursor gas at a third temperature lower
than the second temperature, and
e) optionally, repeating at least once step b) through step d) till a desired layer
thickness is achieved.
2. A method according to claim 1, wherein the semiconductor substrate comprises any semiconductor
material suitable in the field of IC processing.
3. A method according to claim 2, wherein said semiconductor substrate comprises silicon,
germanium or silicon germanium.
4. A method according to any of claims 1 to 3, wherein said first precursor gas is a
halide or an oxyhalide.
5. A method according to claim 4, wherein said halide is a metal halide or said oxyhalide
is a metal oxhyhalide.
6. A method according to claim 4 or 5 wherein said first precursor gas is HfCl4, TaCl5, WF6, WOCl4, ZrCl4, AlCl3, POCl3, TiCl4, or SiCl4.
7. A method according to any of claims 1 to 6, wherein said second precursor gas is any
precursor able to eliminate the ligands of the first precursor.
8. A method according to claim 7 wherein said second precursor gas consists of H2O, H2O2, O2, O3, NH3, H2S, H2Se, PH3, AsH3, C2H4 or Si2H6.
9. A method according to any of claims 1 to 8, wherein said first temperature is comprised
between 100°C and 800°C.
10. A method according to any of claims 1 to 9, wherein said second temperature is substantially
equal or higher than said first temperature.
11. A method according to any of claims 1 to 10 further comprising the step of heating
the substrate surface at a fourth temperature, between step c) and d).
12. A method according to claim 11, wherein said fourth temperature is substantially equal
or higher than the second temperature.
13. A method according to claim 11 or 12, wherein the step of heating the substrate surface
at a fourth temperature is performed in inert atmosphere.
14. A method according to any of claims 1 to 13, wherein said first temperature and said
second temperature are 300°C, and said third temperature is room temperature.
15. A method according to claim 14 wherein, said fourth temperature is 500°C.
16. A method according to any of claims 1 to 15, wherein said substrate is exposed to
a plasma treatment during and/or after step d).
17. A method according to claim 16, wherein said plasma consists of N2O, NO, O2, N2, H2, NO2 or NH3.
18. A method according to any of claims 1 to 17, wherein said first precursor gas is hafnium
tetrachloride and said second precursor gas is H2O.
19. A method according to claim 18, wherein the substrate is exposed to an N2O plasma treatment during and/or after step d).
20. An Atomic Layer Deposition reactor comprising:
- a first and a second susceptor,
- means for heating a substrate when present on the first susceptor, and
- means for cooling the substrate when present on the second susceptor.
21. A reactor according to claim 20 further comprising means for transporting a semiconductor
substrate between both susceptors.
22. A reactor according to claim 20 or 21 further comprising means for producing a plasma.
23. A reactor according to any of claims 20 to 22, wherein said means for heating comprise
any means to create a temperature increase of at least the substrate surface.
24. A reactor according to claim 23, wherein said means for heating are flash lamps.
25. A reactor according to any of claims 20 to 24, wherein said means for cooling comprise
any means to create a temperature decrease of at least the substrate surface.
26. A reactor according to claim 25, wherein said means for cooling is a recirculating
cooling medium or a Peltier element.